CN108568285B - Preparation method of magnetic arsenic-removing solid chelating agent - Google Patents
Preparation method of magnetic arsenic-removing solid chelating agent Download PDFInfo
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Abstract
The invention relates to a magnetic arsenic-removing solid chelating agent powder material and a preparation method thereof, wherein the particle size range is 0.5-500.0 mu m, and the method selects SiO with an internal coating magnetic material2The particles are used as a core-shell material matrix, phosphonic acid functional groups are introduced on a shell layer through surface modification, and metal ions with affinity to arsenic are complexed to prepare the novel magnetic arsenic removal solid chelating agent powder material. The chelating agent has stable structure, wide application range and strong chelating and trapping capacity, can selectively adsorb, separate and enrich arsenic oxide ions in water and soil, soil or a solid-liquid suspension (mixed) system, can be quickly separated from the water, soil and the solid-liquid suspension system by a magnet or a magnetic separation device, is convenient for regeneration and reuse, has low cost, can be widely applied to complex systems such as soil and the like or mineral separation equipment to automatically separate large-scale metal ions, and is suitable for industries such as environmental protection, pollution control, biological separation, mineral separation and the like.
Description
Technical Field
The invention relates to a preparation method of a magnetic arsenic removal solid chelating agent, which can selectively adsorb, separate and enrich arsenic oxide ions in water and soil, soil or a solid-liquid virtual floating (mixing) system. The method belongs to the field of environmental chemistry.
Background
As is a highly toxic, carcinogenic element. Development and smelting of mineral products, use of As-containing pesticides and fertilizers, etc., cause arsenic to enter the environment and accumulate in the soil gradually. Arsenic, like heavy metals, is not readily eliminated after entry into the soil because of its undegradability and relative stability in the environment. As exists mainly in the form of anions in soil, the remediation difficulty of the soil polluted by other heavy metals is higher. As (III) is more toxic to crops than inorganic As (V) in soil. As has high affinity with sulfhydryl, so that As can be combined with protein, amino acid and enzyme containing sulfhydryl to seriously interfere with the biological activity; as atomic structure is similar to phosphorus, increases As in soil, can reduce the absorption of plants to phosphorus, and interferes the metabolic pathway of crops to phosphorus. How to relieve or solve the heavy metal pollution of soil becomes a troublesome problem of global attention.
So far, there are mainly phytoremediation, chemical fixation remediation and chemical extraction remediation. In fact, it takes a long time for plants to restore the soil; the heavy metals in the soil cannot be removed by chemical fixation, and when the soil condition is changed, the heavy metals are in the risk of being dissolved and activated again; chemical extraction, especially with strong acids, can lead to severe damage of soil components. The adsorption method is that solid adsorption material is used to selectively adsorb arsenic oxide ions in the contact process of the solid adsorption material and an arsenic-containing system, and the adsorbed material is eluted and regenerated by acid or alkali, so that the separation and enrichment of the arsenic oxide ions are realized. Sites which are not coordinated with metal ions in the center of the phosphonic acid metal complex have strong chelating and trapping effects on arsenic oxide ions, and can chelate and trap the arsenic oxide ions.
Wei Junying published a paper "high affinity environment of phosphopeptides by magnetic nanoparticles no pads of lipids and zirconium phosphate te f o r phosphate protein analysis" on Rapid communication in Mass Spectrometry, 2008, 22 (7), which produces a lower number of zirconium phosphonate functions and a lower adsorption capacity.
The functional magnetic composite material is formed by coating and modifying a core-shell material matrix which is magnetic SiO2 through a physical and chemical method, and is rapidly separated and recovered under the action of an external magnetic field. In view of the above, the invention intends to combine the characteristic of the super strong selective adsorption effect of the phosphonic acid metal complex on the arsenic oxide ions, and graft the phosphonic acid metal complex on the surface of the magnetic SiO2 microsphere matrix through organic-inorganic hybrid reaction to prepare the functionalized magnetic solid chelating agent with high efficient adsorption performance on the arsenic oxide ions, and the chelating agent has the advantages of high chelating and trapping speed, large adsorption capacity and strong selectivity.
Disclosure of Invention
Aiming at the defects of the prior art, the magnetic arsenic removal solid chelating agent prepared by the invention has the advantages of simple method, low cost, large adsorption capacity and strong selectivity, and can effectively separate and enrich arsenic.
One of the purposes of the invention is to provide a magnetic arsenic removal solid chelating agent; the second purpose of the invention is to provide the application of the magnetic arsenic removal solid chelating agent as an arsenic pollution removal and purification agent for complex systems such as soil and the like.
The technical scheme of the invention comprises the following parts.
A magnetic arsenic removal solid chelating agent powder material takes SiO2 particles coated with magnetic nanoparticles as a magnetic core-shell structure material substrate, a shell layer SiO2 is linked with a phosphonic acid functional group through a covalent bond, the phosphonic acid functional group is complexed with metal ions with affinity to arsenic, and the metal ions with affinity to arsenic are one or more of Cu2+, Fe2+, Fe3+, Zr4+, La3+ and Zn2 +; the magnetic arsenic-removing solid chelating agent powder material is prepared by the following method:
1) preparation of magnetic SiO2 microsphere matrix: adding the magnetic nanoparticles into absolute ethyl alcohol, stirring and dispersing uniformly, adding tetraethoxysilane and ammonia water, stirring for 3-6 hours at the temperature of 20-40 ℃, separating solid particles by using a magnetic field, and washing the magnetic particles by using deionized water and absolute ethyl alcohol to obtain a magnetic SiO2 microsphere matrix.
2) Preparation of amino-functionalized magnetic particles: adding absolute ethyl alcohol into a magnetic SiO2 microsphere matrix, uniformly stirring and dispersing, adding a silane coupling agent, mechanically stirring and refluxing for 6-12 h, cooling, performing suction filtration, washing magnetic particles with deionized water or absolute ethyl alcohol, and modifying with a functional reagent to finally obtain amino functional magnetic particles.
3) Preparing micron-sized phosphonic acid functionalized magnetic particles: adding amino functionalized magnetic particles into absolute ethyl alcohol, stirring and dispersing uniformly, then respectively adding paraformaldehyde, a phosphating reagent and concentrated hydrochloric acid, stirring and refluxing for 5-10 h, cooling, performing suction filtration, and washing magnetic particles with deionized water and absolute ethyl alcohol to obtain the micron-sized phosphonic acid functionalized magnetic particles.
4) Preparing a micron-sized magnetic arsenic removal solid chelating agent: adding the micron-sized phosphonic acid functionalized magnetic particles into a metal ion solution with pH = 1.0-3.0 and affinity to arsenic, mechanically stirring and refluxing for 6-12 h, cooling and then performing suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to obtain the micron-sized magnetic arsenic removal solid chelating agent.
Furthermore, the particle size range of the chelating agent powder material is 0.5-500.0 μm.
Furthermore, the type of the selected magnetic nanoparticles is Fe3O4 or iron powder or NiFe2O4, and the particle size of the magnetic nanoparticles is within 200-500 nm.
A preparation method of a magnetic arsenic removal solid chelating agent powder material comprises the following steps:
1) preparation of magnetic SiO2 microsphere matrix: adding the magnetic nanoparticles into absolute ethyl alcohol, stirring and dispersing uniformly, adding tetraethoxysilane and ammonia water, stirring for 3-6 hours at the temperature of 20-40 ℃, separating solid particles by using a magnetic field, and washing the magnetic particles by using deionized water and absolute ethyl alcohol to obtain a magnetic SiO2 microsphere matrix.
2) Preparation of amino-functionalized magnetic particles: adding anhydrous ethanol into a magnetic SiO2 microsphere matrix, uniformly stirring and dispersing, adding a silane coupling agent, mechanically stirring and refluxing for 6-12 h, cooling, performing suction filtration, washing magnetic particles with deionized water or anhydrous ethanol, modifying with an amino functional reagent to finally obtain amino functional magnetic particles, wherein the amino functional reagent is of the following types: ammonia water or hydrazine hydrate or ethylenediamine or cyclohexanediamine or diethylenetriamine or triethylenetetramine or tetraethylenepentamine.
3) Preparing micron-sized phosphonic acid functionalized magnetic particles: adding amino functionalized magnetic particles into absolute ethyl alcohol, stirring and dispersing uniformly, then respectively adding paraformaldehyde, a phosphating reagent and concentrated hydrochloric acid, stirring and refluxing for 5-10 h, cooling, performing suction filtration, and washing magnetic particles with deionized water and absolute ethyl alcohol to obtain the micron-sized phosphonic acid functionalized magnetic particles.
4) Preparing a micron-sized magnetic arsenic removal solid chelating agent: adding the micron-sized phosphonic acid functionalized magnetic particles into a metal ion solution with the pH = 1.0-3.0, mechanically stirring and refluxing for 6-12 h, cooling and then carrying out suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to obtain the micron-sized magnetic arsenic removal solid chelating agent.
Further, the material charging amount ratio of the magnetic nanoparticles to the tetraethoxysilane is m (magnetic nanoparticles): m (tetraethoxysilane) =1: 2-1: 10.
further, the silane coupling agent used is 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane or 3-mercaptopropyltriethoxysilane or 3-chloropropylpropyltrimethoxysilane or 3-chloropropylpropyltriethoxysilane or vinylethoxysilane or glycidyloxypropyltrimethoxysilane.
Furthermore, the feeding amount of the amino functionalized magnetic particles, the paraformaldehyde, the phosphating reagent and the concentrated hydrochloric acid is n (the amino functionalized magnetic particles): n (paraformaldehyde): n (phosphating agent): n (concentrated hydrochloric acid) =1: 2:2: 2-1: 15:15: 7; reaction solvent: water or absolute ethyl alcohol or absolute formaldehyde; reaction temperature: 50-120 ℃; the types of phosphating agents used were: phosphoric acid or phosphorus oxychloride or phosphorous acid or triethyl phosphite or triethyl phosphate.
The magnetic arsenic removal solid chelating agent can be applied to the fields of removing arsenic in purified water and heavy metal ions in industrial wastewater, drinking water, farmland soil and lake bottom sludge.
The invention has the beneficial effects that:
(1) the micron-sized magnetic arsenic-removing solid chelating agent prepared by the invention has the advantages of simple and feasible preparation method, reusability and low cost;
(2) the micron-sized magnetic arsenic-removing solid chelating agent has a micron-sized structure, is stable in structure, is a soft magnetic material, and can accelerate the separation speed and realize quick separation and recovery;
(3) the functionalized magnetic solid chelating agent prepared by the technology contains a large amount of phosphonic acid-containing functional groups, has the characteristics of large adsorption capacity, selective adsorption of the phosphonic acid metal complex on arsenic, high adsorption speed and capability of effectively separating and enriching arsenic oxide ions.
Detailed Description
In order that the invention may be better understood, the invention will now be further illustrated by reference to the following specific examples. The technical scheme of the invention comprises but is not limited to the following specific embodiments and any combination of the specific embodiments. In particular to the selection of the compound types, the adjustment of the feed material proportion, the reaction temperature and the like.
Example 1
1) Adding 4g of magnetic NiFe2O4 nanoparticles with the particle size of 200nm into 50mL of absolute ethanol, stirring and dispersing uniformly, adding 5g of tetraethoxysilane and 6mL of ammonia water, continuously stirring and reacting for 3h at 40 ℃, and separating solid particles by using a magnetic field. And washing the magnetic particles for multiple times by using deionized water and absolute ethyl alcohol, and drying to obtain the magnetic NiFe2O4@ SiO2 microsphere matrix.
2) Adding 5g of magnetic NiFe2O4@ SiO2 microsphere matrix into 60mL of absolute ethyl alcohol, stirring and dispersing uniformly, adding 1g of 3-chloropropyltriethoxysilane, continuously stirring and reacting at 50 ℃ for 6h, and separating solid particles by using a magnetic field. And washing the magnetic particles for multiple times by using deionized water and absolute ethyl alcohol, and drying to obtain the chloro-functionalized magnetic particles.
3) Adding 6g of chloro-functionalized magnetic particles into 70mL of absolute ethanol, stirring and dispersing uniformly, adding 6mL of cyclohexanediamine, stirring and reacting at room temperature for 6h, and separating solid particles by using a magnetic field. And washing the magnetic particles with deionized water and absolute ethyl alcohol, and drying to obtain the amino functionalized magnetic particles.
4) Adding 7g of amino functionalized magnetic particles into 80mL of absolute ethyl alcohol, and adding 7.25 g of sodium phosphite, 8g of concentrated hydrochloric acid and 7g of paraformaldehyde; stirring and refluxing for 10h at 60 ℃, cooling, performing suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to finally obtain the micron-sized phosphonic acid functionalized magnetic particles.
5) Adding 10g of phosphonic acid functionalized magnetic particles to 200mL of a saturated FeCl3 solution with pH = 1.0; stirring and refluxing for 10h at 40 ℃, cooling, performing suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to finally obtain the micron-sized magnetic arsenic-removing solid chelating agent with the particle size range of 0.5-100 mu m.
6) Source and collection of test soil: the soil contaminated by arsenic for test adopted in the research comes from the peripheral farmland of a realgar mining area in Shimen county in Hunan province, a soil-drilling sampling method is adopted, 0-25 cm of surface soil is taken, the taken farmland soil is subjected to impurity removal, and the farmland soil is sieved by a 10-mesh sieve for later use.
7) Under the conditions that the water content of soil is 150%, the addition amount of the micron-sized magnetic arsenic removal solid chelating agent is 5% of the mass of the soil, and the pH = 6.5 of slurry, mechanically stirring for 5 hours, magnetically separating and recovering the solid chelating agent, and detecting to find that the removal rate of As reaches 26.7%.
Example 2
1) Adding 3g of magnetic NiFe2O4 nanoparticles with the particle size of 300nm into 50mL of absolute ethanol, stirring and dispersing uniformly, adding 6g of tetraethoxysilane and 7mL of ammonia water, continuously stirring and reacting at 20 ℃ for 6h, and separating solid particles by using a magnetic field. And washing the magnetic particles for multiple times by using deionized water and absolute ethyl alcohol, and drying to obtain the magnetic NiFe2O4@ SiO2 microsphere matrix.
2) Adding 4g of magnetic NiFe2O4@ SiO2 microsphere matrix into 60mL of absolute ethyl alcohol, stirring and dispersing uniformly, adding 1g of 3-chloropropyltriethoxysilane, continuously stirring and reacting at 20 ℃ for 12h, and separating solid particles by using a magnetic field. And washing the magnetic particles for multiple times by using deionized water and absolute ethyl alcohol, and drying to obtain the chloro-functionalized magnetic particles.
3) Adding 5g of chloro-functionalized magnetic particles into 70mL of absolute ethyl alcohol, stirring and dispersing uniformly, adding 6mL of ethylenediamine, stirring and reacting at room temperature for 8h, and separating solid particles by using a magnetic field. And washing the magnetic particles with deionized water and absolute ethyl alcohol, and drying to obtain the amino functionalized magnetic particles.
4) Adding 7g of amino functionalized magnetic particles into 80mL of absolute ethyl alcohol, and adding 9.25 g of sodium phosphite, 6g of concentrated hydrochloric acid and 10g of formaldehyde solution; stirring and refluxing for 10h at 80 ℃, cooling, performing suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to finally obtain the micron-sized phosphonic acid functionalized magnetic particles.
5) Adding 10g of phosphonic acid functionalized magnetic particles to 200mL of saturated FeCl3 solution with pH = 2.0; stirring and refluxing for 10h at 40 ℃, cooling, performing suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to finally obtain the micron-sized magnetic arsenic-removing solid chelating agent with the particle size of 200-300 mu m.
6) And (3) respectively adding 20g of micron-sized magnetic arsenic-removing solid chelating agent into 200mL of solution containing 20mg/L of As (III) and As (V), mechanically stirring for 5h at normal temperature, magnetically separating and recovering the solid chelating agent, and detecting to find that the solution hardly contains As (III) and As (V).
Example 3
1) Adding 4g of magnetic NiFe2O4 nanoparticles with the particle size of 500nm into 50mL of absolute ethanol, stirring and dispersing uniformly, adding 6g of tetraethoxysilane and 7mL of ammonia water, continuously stirring and reacting for 4h at 30 ℃, and separating solid particles by using a magnetic field. And washing the magnetic particles for multiple times by using deionized water and absolute ethyl alcohol, and drying to obtain the magnetic NiFe2O4@ SiO2 microsphere matrix.
2) Adding 5g of magnetic NiFe2O4@ SiO2 microsphere matrix into 60mL of absolute ethyl alcohol, stirring and dispersing uniformly, adding 1.5 g of 3-chloropropyltriethoxysilane, continuously stirring and reacting at 50 ℃ for 8 hours, and separating solid particles by using a magnetic field. And washing the magnetic particles for multiple times by using deionized water and absolute ethyl alcohol, and drying to obtain the chloro-functionalized magnetic particles.
3) Adding 6g of chloro-functionalized magnetic particles into 70mL of absolute ethanol, stirring and dispersing uniformly, adding 6mL of cyclohexanediamine, stirring and reacting at room temperature for 10h, and separating solid particles by using a magnetic field. And washing the magnetic particles with deionized water and absolute ethyl alcohol, and drying to obtain the amino functionalized magnetic particles.
4) Adding 7g of amino functionalized magnetic particles into 80mL of absolute ethyl alcohol, and adding 7.25 g of sodium phosphite, 10g of concentrated hydrochloric acid and 9g of paraformaldehyde; stirring and refluxing for 10h at 120 ℃, cooling, performing suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to finally obtain the micron-sized phosphonic acid functionalized magnetic particles.
5) Adding 10g of phosphonic acid functionalized magnetic particles to 200mL of a saturated FeCl3 solution with pH = 3.0; stirring and refluxing for 10h at 40 ℃, cooling, performing suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to finally obtain the micron-sized magnetic arsenic-removing solid chelating agent with the particle size of 400-500 mu m.
6) Taking the lake bottom sludge polluted by arsenic, mechanically stirring the lake bottom sludge for 5 hours under the condition that the addition amount of the micron-sized magnetic arsenic removal solid chelating agent is 5% of the soil mass, and the pH = 6.1 of the slurry, magnetically separating and recovering the solid chelating agent, and detecting to find that the removal rate of As reaches 35.3%.
Claims (8)
1. A magnetic arsenic removal solid chelating agent powder material is characterized in that: SiO with magnetic nano-particle coated inside2 Particles as magnetic core-shellsStructural material substrate, shell SiO2 Having covalently linked phosphonic acid functions complexing a metal ion having affinity for arsenic, said metal ion having affinity for arsenic being Cu2+ Or Fe2+ Or Fe3+ Or Zr4+ Or La3+ Or Zn2+ One or more of; the magnetic arsenic-removing solid chelating agent powder material is prepared by the following method:
1) magnetic SiO2 Preparing a microsphere matrix: adding the magnetic nanoparticles into absolute ethyl alcohol, stirring and dispersing uniformly, adding tetraethoxysilane and ammonia water, stirring for 3-6 hours at the temperature of 20-40 ℃, separating solid particles by using a magnetic field, and washing the magnetic particles by using deionized water and absolute ethyl alcohol to obtain magnetic SiO2 A microsphere matrix;
2) preparation of amino-functionalized magnetic particles: magnetic SiO2 Adding absolute ethyl alcohol into a microsphere matrix, uniformly stirring and dispersing, adding a silane coupling agent, mechanically stirring and refluxing for 6-12 hours, cooling, performing suction filtration, washing magnetic particles with deionized water or absolute ethyl alcohol, modifying with an amino functional reagent, and finally obtaining amino functional magnetic particles, wherein the amino functional reagent is of the following types: ammonia water or hydrazine hydrate or ethylenediamine or cyclohexanediamine or diethylenetriamine or triethylenetetramine or tetraethylenepentamine; the silane coupling agent is 3-chloro propyl trimethoxy silane or 3-chloro propyl triethoxy silane;
3) preparing micron-sized phosphonic acid functionalized magnetic particles: adding amino functionalized magnetic particles into absolute ethyl alcohol, stirring and dispersing uniformly, then respectively adding paraformaldehyde, a phosphating reagent and concentrated hydrochloric acid, stirring and refluxing for 5-10 h, cooling, then performing suction filtration, and washing magnetic particles with deionized water and absolute ethyl alcohol to obtain micron-sized phosphonic acid functionalized magnetic particles;
4) preparing a micron-sized magnetic arsenic removal solid chelating agent: adding the micron-sized phosphonic acid functionalized magnetic particles into a metal ion solution with pH = 1.0-3.0 and affinity to arsenic, mechanically stirring and refluxing for 6-12 h, cooling and then performing suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to obtain the micron-sized magnetic arsenic removal solid chelating agent.
2. The magnetic arsenic removal solid chelating agent powder material as claimed in claim 1, wherein: the particle size range is 0.5 to 500.0 μm.
3. The magnetic arsenic removal solid chelating agent powder material as claimed in claim 1, wherein: the kind of the selected magnetic nano-particles is Fe3 O4 Or iron powder or NiFe2 O4 The particle size is within 200-500 nm.
4. A preparation method of a magnetic arsenic removal solid chelating agent powder material is characterized by comprising the following steps:
1) magnetic SiO2 Preparing a microsphere matrix: adding the magnetic nanoparticles into absolute ethyl alcohol, stirring and dispersing uniformly, adding tetraethoxysilane and ammonia water, stirring for 3-6 hours at the temperature of 20-40 ℃, separating solid particles by using a magnetic field, and washing the magnetic particles by using deionized water and absolute ethyl alcohol to obtain magnetic SiO2 A microsphere matrix;
2) preparation of amino-functionalized magnetic particles: magnetic SiO2 Adding absolute ethyl alcohol into a microsphere matrix, uniformly stirring and dispersing, adding a silane coupling agent, mechanically stirring and refluxing for 6-12 hours, cooling, performing suction filtration, washing magnetic particles with deionized water or absolute ethyl alcohol, modifying with an amino functional reagent, and finally obtaining amino functional magnetic particles, wherein the amino functional reagent is of the following types: ammonia water or hydrazine hydrate or ethylenediamine or cyclohexanediamine or diethylenetriamine or triethylenetetramine or tetraethylenepentamine; the silane coupling agent is 3-chloro propyl trimethoxy silane or 3-chloro propyl triethoxy silane;
3) preparing micron-sized phosphonic acid functionalized magnetic particles: adding amino functionalized magnetic particles into absolute ethyl alcohol, stirring and dispersing uniformly, then respectively adding paraformaldehyde, a phosphating reagent and concentrated hydrochloric acid, stirring and refluxing for 5-10 h, cooling, then performing suction filtration, and washing magnetic particles with deionized water and absolute ethyl alcohol to obtain micron-sized phosphonic acid functionalized magnetic particles;
4) preparing a micron-sized magnetic arsenic removal solid chelating agent: adding the micron-sized phosphonic acid functionalized magnetic particles into a metal ion solution with pH = 1.0-3.0 and affinity to arsenic, mechanically stirring and refluxing for 6-12 h, cooling and then performing suction filtration, and washing the magnetic particles with deionized water and absolute ethyl alcohol to obtain the micron-sized magnetic arsenic removal solid chelating agent.
5. The method for preparing the magnetic arsenic removal solid chelating agent powder material as claimed in claim 4, wherein the method comprises the following steps: the feeding amount ratio of the magnetic nanoparticles to the tetraethoxysilane is 1: 2-1: 10.
6. the method for preparing the magnetic arsenic removal solid chelating agent powder material as claimed in claim 4, wherein the method comprises the following steps: the types of phosphating agents used were: phosphoric acid or phosphorus oxychloride or phosphorous acid or triethyl phosphite or triethyl phosphate.
7. The method for preparing the magnetic arsenic removal solid chelating agent powder material as claimed in claim 4, wherein the method comprises the following steps: the reaction temperature is 50-120 ℃.
8. Use of the magnetic arsenic removal solid chelating agent powder material as claimed in claim 1, 2 or 3 for removing arsenic from purified water.
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| CN110711557A (en) * | 2019-11-21 | 2020-01-21 | 云南大学 | Preparation method and application of multi-step modified nano porous silicon adsorbent for As |
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| CN101530766B (en) * | 2009-03-19 | 2011-06-08 | 吉林大学 | Method for preparing amino functional magnetic fluorescent coding microsphere with double-nucleocapsid structure |
| KR20140010953A (en) * | 2011-02-22 | 2014-01-27 | 에보니크 데구사 게엠베하 | Process for preparing aqueous colloidal silica sols of high purity from alkali metal silicate solutions |
| CN103028351B (en) * | 2012-12-04 | 2014-09-03 | 天津大学 | Benzene sulfonic acid modified magnetic microsphere and preparation method and application thereof |
| CN103073170B (en) * | 2013-01-15 | 2014-05-07 | 中国地质大学（武汉） | Deep sludge dehydrated method based on magnetic super-strong absorbent |
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